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Патент USA US3093686

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United States Patent 0
P atented June 11, 1963
the wash water is neutral to litmus. The solution is then
dried with magnesium sulfate, ?ltered and evaporated to
John G. Abramo and Earl C. Chapin, Spring?eld, Mass,
assignors to Monsanto Chemical Company, St. Louis,
maining is recrystallized with ethanol. The white solid
which results analyzes correctly for 1-(alpha-cyanoethyl)
Mo., a corporation of Delaware
dryness in an evaporating dish. The solid material re
Example III
A solution of v60 grams of p-(alpha-chloroisopropyl)
The‘ present invention relates to aromatic compounds 10 benzyl chloride in 150 ml. of_ 95% alcohol is added drop
wise to a, solution of 35 grams of sodium cyanide in 100
and more particularly to the production of alpha-cyano
ml. of water and 100 ml. of ethanol maintained under stir
alkyl-aromatic-methyl cyanides having the structure:
ring and re?uxing. After addition is completed, re?uxing
and stirring are continued for 3 hours. The reaction mix
ture, which is a dark liquid at this point, is ?ltered, poured
No Drawing. Filed May 18, 1959, Ser. No. 813,636
2 Claims. (Cl. 260-465)
into a separatory funnel and extracted with three 150 ml.
portions of benzene. The benzene extracts are collected
and washed 3 times with 200 ml. portions of water. Dis
wherein Ar is an aromatic hydrocarbon and R is selected
tillation of the benzene is then carried out in a distillation
from the class consisting of hydrogen and methyl radical.
apparatus evacuated to 20 ml. of Hg pressure. After the
Accordingly, it is ‘a principal object of this invention 20 benzene has been distilled, the pressure in the apparatus
to produce alpha-cyanoalkyl-aromatic-methyl cyanides.
is lowered to 0.3 mm. Hg pressure and distillation con
Another object is to provide a simple method by which
to provide these dicyanides.
tinued. A small amount of liquid boiling up to 155° C.
is collected and discarded, and the ‘main fraction boiling
_ ,
Other objects of the invention will in part be obvious
and will in part appear hereinafter.
155° to 163° C. at 0.3 mm. Hg is collected and analyzed.
25 Elemental and infrared analysis are consistent with the
The objects of the invention are attained by reacting Ian
expected values for p-(alpha-cyanoisopropyl)benzyl cy
‘alpha-haloalkyl-aromatic-methyl halide, having the struc
The alpha-cyanoalkyl-aromatic-methyl cyanides of the
with a base metal cyanide in a suitable medium, wherein 35
can be produced by reacting (a) the corresponding alpha
throughout Ar is an aromatic radical, R is selected from
the class consisting of hydrogen and methyl radical and
X and X1 are halogens.
present invention having the structure:
halomethyl compound more particularly an alpha-halo
alkyl-aromatic-methyl halide of the structure:
The following examples are given in illustration of the
invention. Where parts are mentioned, parts by weight 40
are intended unless otherwise described.‘
Example I
Ninety-?ve grams of p-(a1pha-chloroethyl)benzyl chlo
ride is added dropwise over a period of one hour to a
‘with (b) a base metal cyanide, wherein throughout Ar
solution of 75 grams of sodium cyanide in 250 ml. of 45 is an aromatic radical, R is’selected from the class con
water and 250 ml. of methanol. The reaction mixture is' ' sisting of hydrogen and methyl radical and X and X1
are halogens. .
then heated to re?ux temperature and held for 7 hours.
The simplest examples of the sponsored cyanides, more
At the end of this period, the reaction mixture which is
speci?cally ldicyanides, are the o-, rn-, and p-( alpha-cyano<
very dark colored is diluted with 500 ml. of water and
extracted‘with ?ve 150 ml. portions of benzene. ‘ The ben 50 ethyD-benzyl cyanides. here R is a methyl radical, these
are the o-, m~, and p-“(alpha-cyanoisopropyl)benzyl cyan
zene extracts are combined and washed with water until
ides. With variations carried‘ out in the‘ aromatic radical
the wash water is‘ neutral to litmus paper. The washed
Ar, as for example when this radical is a 'biphenyL' naph
extract is then dried over magnesium sulfate. The desic- ‘
thyl, or anthryl radical, additional dicyanide products re
cant is ?ltered off and benzene is removed by distillation.
sult. Examples of these include alpha-cyanoethylnaph
The product is distilled under vacuum after the benzene
thyl-methyl cyanides, alpha-cyanoethylanthryl-methyl cy
has been distilled off and following a small amount of
anides, and when the alkyl cyanide substituent is an iso
fore-run, 20 grams of a colorless liquid boiling at 143°
propyl group representative products are the alpha-cyano
C./ 0.4 mm. Hg are collected. Elemental analysis and in
frared analysis identify this material as p-(alpha-cyano
ethyl)benzyl cyanide.
Example II
A solution of 510 grams of sodium cyanide in 200 ml.
of water and 200 ml. of methanol is heated to 50° C.
Fifty grams of l-(alphaschloroethyl)-4-(chloromethyl)
isopropylbiphenyl-methyl cyanides, alpha-cyanoisopropyl
naphthyl-methyl cyanides and alpha-cyanoisopropylan
th-ryl-methyl cyanides including the various isomers of the
preceding which result from variations practiced in the
positioning of the two major substituents, to wit: (1) the
alpha-cyanoalkyl substituent which can be either an alpha
65 cyanoethyl radical or an alpha-cyanoisopropyl radical and
naphthalene is then added in small portions over a one
(2) the cyanomethyl substituent. In the matter of sub_
hour period. The reaction mixture is maintained at 50°
stituents, additional nuclear substituents of a secondary
C. for 6 hours after addition has been completed. At the
nature, such as halogens and alkyl radicals, the latter rep
end of this period the mixture is ?ltered in a Biichner fun
resented by methyl, ethyl, and the like, can be accom
nel to remove precipitated salts, diluted with 200 ml. of 70 modate on the various aromatic radicals indicated by the
water and extracted with three 100 ml. portions of ben
symbolv Ar.
The benzene extracts are washed with water until
The corresponding alpha-haloalkyl-aromatic-methyl hal
ides which can serve as starting materials from which to
for using an amount of base metal cyanide in excess of
obtain the desired cyanide products of the present inven
twice the molar amount of halomethyl-aromatic-methyl
tion have the structure:
halide to be reacted. The temperature at which the re
action can be carried out ranges generally between 50°
200° C. with a further preference of 90°—-11\0° C. It is
further suggested that the reaction be carried out under
re?ux conditions and while subatmospheric, atmospheric
or superatrnospheric pressure conditions can be used at
wherein Ar is an aromatic radical, R is selected from the
mospheric pressure is most desirable.
The alpha-cyanoalkyl-aromatic-methyl cyanides of the
class consisting of hydrogen and methyl radical and X 10
present invention can be subjected to hydrolysis reactions
and X1 are halogens. The halogen symbolized as X1,
to produce difunctional aromatic materials, the functional
contained in the haloalkyl substituent (either haloethyl or
groups of which are carboxylic in nature. These then can
haloisopropyl), is in the alpha position. In either case,
be used in condensation reactions with diols and diamines
X or X1, can be bromine, chlorine, ?uorine or iodine but
which to produce synthetic polymeric materials hav
are preferably chlorine. Illustrative of the haloalkyl
ing particular usefulness in ?lm, ?ber and surface coating
aromatic-methyl halides which can be used is the p-(alpha
applications. Additionally, the alpha-cyanoalkyl-aromat
chloroethyl)benzyl chloride which is used to produce p—
ic-methyl cyanides of the present invention can be used
(alpha-cyanoethyl)benzyl cyanide. The dihalide starting
singly or in mixture with their beta-isomer counterparts
materials can be produced by a two-step process in which
disclosed and claimed in our copending application S.N.
(a) the corresponding alkyl-aromatic hydrocarbon is halo
768,826 ?led October 22, 1958, now abandoned.
methylated to yield the corresponding alkyl-aromatic-halo
It will thus be seen that the objects set forth above
methyl compound which is (b) then halogenated to the
those made apparent from the preceding descrip
corresponding alpha-haloalkyl-arornatic-halomethyl com
tion are e?iciently attained, and since certain changes may
pound. To illustrate, ethyl benzene is chloromethylated
to yield p-ethylbenzyl chloride and subsequent chlorina 25 be made in carrying out the above process and in the
dicyanide products, without departing from the scope of
tion yields p-‘(alpha-chloroethyl)benzyl chloride. Other
invention, it is intended that all matter contained in
alpha-haloalkyl-aromatic-methyl halides can be obtained
the above description shall be interpreted as illustrative
in this manner for use as starting materials.
and not in a lirnting sense.
As previously described, the desired dicyanide can be
obtained by causing a corresponding alpha-haloalkyl-aro 30 What is claimed is:
1. A class of alpha-cyanoalkyl-aromatic methyl cyan
matic-methyl halide to react with a base metal cyanide in
ides having the structure:
the presence of a solvent for the reactants. The base
metal cyanides include the alkali metal cyanides such as
sodium cyanide, potassium cyanide, lithium cyanide, etc.,
alkaline earth metal cyanides such as calcium cyanide, 35
barium cyanide, strontium cyanide and the like.
In a
lesser preferred embodiment, ‘an alpha-haloalkyl-aromatic
methyl halide corresponding to the desired dicyanide is
wherein Ar is an aromatic hydrocarbon radical selected
caused to react with hydrogen cyanide in the presence of
from the class consisting of naphthylene and anthrylene
an ‘acid acceptor such as the carbonate of one of the above 40 and R is selected from the class consisting of hydrogen and
metals. The solvent can be water or various organic
the methyl radical.
solvents such as methanol, ethanol, acetone, methyl ethyl
ketone and mixtures of the same. Their choice will be
re?ective of the desired temperatures of reaction and sol
vent properties in relation to the reactants. The use of 45
the term “solvent” does not indicate that the reactants
must be completely solvated in the same. Rather it indi
cates a medium which allows sui?cient contact between
reactants as to permit reaction to take place. Potassium
2. 1- ( alpha-cyanoethyl ) ~4- (cyanomethyl ) naphthalene.
References Cited in the ?le of this patent
Kirk _________________ __ Feb. 14, 1950
Copelin et al ___________ __ Ian. 29, 1957
Berther ______________ _._ Dec. 29, 1959
Germany _____________ __ Mar. 5, 1953
cyanide and sodium cyanide perform well as the base 50
metal cyanide in the presence of water or a mixture of
water and ethanol. The amount of base metal cyanide to
be used is determined by the number of displaceable halo
gens on the principal substituents of the haloalkyl-aro
Beilstein, Handbook der Organischen Chemie, volume
matic-methyl halide starting material. These are two in 01 U'' 9, pages 874-875 (1926); volume 9, Second Supplement,
In addition, it is well to use an excess of the
cyanide. Consequently then the preferred procedure calls
page 632 '(1949).
(Copies of above in Sci. Library.)
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